One-pot synthesis of cyclophane-type macrocycles using manganese(iii)-mediated oxidative radical cyclization

Ito, Yosuke; Tomiyasu, Yuichi; Kawanabe, Takahiro; Uemura, Keisuke; Ushimizu, Yuu; Nishino, Hiroshi

doi:10.1039/c0ob00683a

Cited by 18 publications

(2 citation statements)

References 90 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, the mechanism for the formation of 3 would be explained as follows (Scheme ); Mn(III)‐enolate complex A produced in situ by the reaction of pyrrolidinedione 1 with Mn(OAc) 3 underwent single‐electron transfer oxidation to give pyrrolidinedione radical B . Because the pyrrolidinedione radical B is electron‐poor, the radical B should inevitably be attacked by electron‐rich alkene 2 via the electron donor‐acceptor‐like complex to furnish tertiary radical C , which is easily trapped by dissolved molecular oxygen, giving peroxy radical D . The resulting peroxy radical intermediate D is reduced by the Mn(II) species to yield peroxy‐Mn(III) complex E , which undergoes protonation with acetic acid and regeneration of the Mn(III) species to conclude the catalytic cycle and to provide hydroperoxide F .…”

Section: Resultsmentioning

confidence: 99%

Mn(III)‐catalyzed Aerobic Oxidation of 3‐Alkyl‐4‐hydroxy‐1H‐pyrrol‐2(5H)‐ones in the Presence of 1,1‐Diarylethenes. Synthesis of Stable 8‐Aza‐1‐hydroxy‐2,3‐dioxabicyclo[4.3.0]nonan‐7‐one Framework

Haque

Nishino

2013

Journal of Heterocyclic Chem

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

Mn(III)‐catalyzed Aerobic Oxidation of 3‐Alkyl‐4‐hydroxy‐1H‐pyrrol‐2(5H)‐ones in the Presence of 1,1‐Diarylethenes. Synthesis of Stable 8‐Aza‐1‐hydroxy‐2,3‐dioxabicyclo[4.3.0]nonan‐7‐one Framework

Haque

Nishino

2013

Journal of Heterocyclic Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…37 Cyclophane-type 21-56 membered macrocyclic compounds 54a(n)Ar-54b(n)Ar, bearing two fused substituted dihydrofuran rings were synthesized by the Mn(III)-mediated oxidative addition of terminal dienes 52a-52b and bis(3-oxobutanoate) containing aromatic compounds 55(n)Ar, under high dilution conditions (Scheme 15). 38 The mechanism involves intermolecular mono-cyclization of terminal dienes with the manganese(III)-enolate complex of 1,3-dicarbonyl moiety, followed by the intramolecular dihydrofuranation reaction.…”

Section: Synthesis Of Furans and Derivativesmentioning

confidence: 99%

Recent advances in manganese(iii) acetate mediated organic synthesis

2013

View full text Add to dashboard Cite

The preceding four decades have witnessed a major expansion in the field of free-radical assisted reactions, as they are becoming a key tool in organic, polymer and complex natural product chemistry. This progress has clearly changed the traditional idea of free-radical reactions being ''extremely uncontrollable'', thereby allowing chemists to deal with free radicals in a more accurate and controlled way.Manganese(III) acetate mediated radical reactions have reached distinction in this field, as a wide range of protocols involving manganese(III) acetate under mild and efficient reaction conditions have been developed for the synthesis of biologically active and important organic molecules through oxidation, addition and cyclization reactions, which are in general difficult to achieve by the established synthetic operations. The present review focuses on manganese(III) acetate mediated oxidative free-radical reactions that have been developed and adapted during the last five years. It includes the advancements made in the field of free-radical promoted carbon-carbon and carbon-oxygen bond forming reactions, illustrating the examples of furans, hydrofurans, pyrroles, bicyclic lactones, biaryls, oxepins, indole-alkaloids, 1,2benzanthracene and C 60 -fused tetrahydronaphthalene synthesis. Numerous manganese(III) acetate initiated carbon-phosphorus bond formation reactions were also devised during recent years, involving both phosphonyl and phosphinoyl radicals, and are a key part of this review. Manganese(III) acetate promotes functionalization of significant organic compounds, thereby guiding the synthesis of important and complex molecules, such as the formation of propellanes, quinolinones, 1,2-dioxalanes; oxidation of indoles; lactonization of fullerene [C 60 ], malonyl cyclopentanes, glycols; and hydroperoxidation of heterocycles. The review will also envelop several recent milestones that have been achieved in the chemistry of natural products pre ´cising the vital role of manganese(III) acetate in the key synthetic steps.

show abstract

Mn(III)‐Based Oxidative Cyclization of Alkenes Using Tricarbonyl System

et al. 2018

Self Cite

View full text Add to dashboard Cite

The Mn(III)-based oxidation of 1,1-disubstituted ethenes with 2-(2-aryl-2-oxoethyl)malonates, 2-acetyl-4-aryl-4-oxobutanoates, and 3-acetyl-1-arylpentane-1,4-diones was evaluated. The reaction using the malonates mainly gave the 2,3-dihydro-4Hpyran-4,4-dicarboxylates along with g-lactones. A similar reaction using the acetyloxobutanoates and acetylpentanediones produced the 2,3,3a,6a-tetrahydrofuro[2, 3-b]furans and the corresponding dihydropyrans. The cyclization was strongly affected by the nucleophilicity of the carbonyl oxygen in the carbocation intermediate, and the kinetic and thermodynamic controls of the following reaction. The structure determination and the mechanisms are discussed.[a] T.

show abstract

One-pot synthesis of cyclophane-type macrocycles using manganese(iii)-mediated oxidative radical cyclization

Cited by 18 publications

References 90 publications

Mn(III)‐catalyzed Aerobic Oxidation of 3‐Alkyl‐4‐hydroxy‐1H‐pyrrol‐2(5H)‐ones in the Presence of 1,1‐Diarylethenes. Synthesis of Stable 8‐Aza‐1‐hydroxy‐2,3‐dioxabicyclo[4.3.0]nonan‐7‐one Framework

Mn(III)‐catalyzed Aerobic Oxidation of 3‐Alkyl‐4‐hydroxy‐1H‐pyrrol‐2(5H)‐ones in the Presence of 1,1‐Diarylethenes. Synthesis of Stable 8‐Aza‐1‐hydroxy‐2,3‐dioxabicyclo[4.3.0]nonan‐7‐one Framework

Recent advances in manganese(iii) acetate mediated organic synthesis

Mn(III)‐Based Oxidative Cyclization of Alkenes Using Tricarbonyl System

Contact Info

Product

Resources

About